CN112403520A - Preparation and application of vermiculite supported phosphotungstic acid green catalyst - Google Patents
Preparation and application of vermiculite supported phosphotungstic acid green catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 80
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000010455 vermiculite Substances 0.000 title claims abstract description 47
- 229910052902 vermiculite Inorganic materials 0.000 title claims abstract description 47
- 235000019354 vermiculite Nutrition 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000011230 binding agent Substances 0.000 claims abstract description 27
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 21
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000004115 Sodium Silicate Substances 0.000 claims abstract description 4
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims abstract description 4
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims abstract description 4
- 239000001488 sodium phosphate Substances 0.000 claims abstract description 4
- 229910000162 sodium phosphate Inorganic materials 0.000 claims abstract description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 4
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims abstract description 4
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 239000010410 layer Substances 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 12
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 238000011068 loading method Methods 0.000 claims description 9
- 238000005341 cation exchange Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- 239000011964 heteropoly acid Substances 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000012044 organic layer Substances 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 239000000126 substance Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 description 10
- 238000000034 method Methods 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 229910018512 Al—OH Inorganic materials 0.000 description 2
- 229910008051 Si-OH Inorganic materials 0.000 description 2
- 229910006358 Si—OH Inorganic materials 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000007171 acid catalysis Methods 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- DKIGIIRBUVYQEC-UHFFFAOYSA-N cyclohexanol;cyclohexene Chemical compound C1CCC=CC1.OC1CCCCC1 DKIGIIRBUVYQEC-UHFFFAOYSA-N 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of chemical industry, and particularly relates to a preparation method and application of a vermiculite supported phosphotungstic acid green catalyst, wherein phosphotungstic acid is used as an active species, high-temperature roasted sulfuric acid modified vermiculite is used as a carrier, one of sodium hexametaphosphate, sodium phosphate and sodium silicate is used as a binder to prepare the phosphotungstic acid supported catalyst, the phosphotungstic acid supported catalyst is applied to research of a heterogeneous reaction system for preparing cyclohexene by dehydrating cyclohexanol, when the binder dosage is 0.3 g, the phosphotungstic acid is 0.6 g, the modified vermiculite is 1 g, and the catalyst dosage is 0.6 g, the cyclohexene selectivity is 100%, the yield reaches 93.70%, the catalyst can be recycled after the reaction is finished, and the catalyst still has high yield after being reused for 8 times.
Description
Technical Field
The invention relates to a preparation method and application of a vermiculite supported phosphotungstic acid green catalyst, and belongs to the technical field of chemical industry.
Background
Cyclohexene as an important organic chemical intermediate raw material is commonly used for synthesizing pesticides, medicines and high polymers, is used for preparing catalysts and solvents in chemical production, and is used as an extracting agent and a high-survival-value stabilizer in the petroleum industry, and has large demand and wide application. In the conventional industrial production of cyclohexene cyclohexanol is usually prepared by liquid phase dehydration of cyclohexanol using concentrated sulfuric acid as catalyst. Concentrated sulfuric acid as a catalyst has the defects of equipment corrosion, serious carbonization, low yield (70 percent), environmental pollution, difficult catalyst recycling and the like. With the introduction of the concept of "green chemistry" and the improvement of environmental protection in recent years, it has become necessary to seek to develop a novel green heterogeneous recyclable catalyst.
Recent research at home and abroad shows that the heteropoly acid has a determined structure, simultaneously has acidity and oxidizability, can be used as an acid-base, redox or bifunctional catalyst, and can systematically regulate and control the performance of the catalyst by selecting constituent elements (coordination atoms, central atoms, counter ions and the like) under the condition of not changing the structure of heteropolyanions. In solid phase catalytic reactions, polar molecules can enter the catalyst bulk phase, with a "pseudo-liquid phase" behavior that makes the entire bulk phase a reaction field. Therefore, the catalyst has the characteristics of high activity, good selectivity, slight corrosion, mild reaction conditions and the like.
Phosphotungstic acid (H)3PW12O40·nH2O) oxygen-containing polyacid which is formed by coordination bridging of heteroatom P and coordination atom W through oxygen atoms in a certain structure has a Keggin structure, has both acid catalysis and oxidation catalysis functions, is protonic acid with uniform strength, and has high catalytic activity. Due to the poleThe catalyst is easy to dissolve in polar solvent and is difficult to be used as a solid acid catalyst in a polar reaction system, and the defects of easy sintering at high temperature, easy carbon deposition and inactivation on the surface, uneven acid strength distribution and the like exist, so that the industrial application of the catalyst is limited. In order to overcome the above-mentioned drawbacks, it is generally carried on a suitable carrier to increase the specific surface area and to improve the dispersion of the active ingredient. The common carriers comprise alumina, silica gel, silica, activated carbon, diatomite, montmorillonite and the like, and compared with the carriers, the vermiculite has the characteristics of large crystal grain, easiness in expansion, high temperature resistance, large specific surface area and the like, but the expanded vermiculite is rarely reported as the carrier.
The vermiculite is a layered silicate mineral with a 2:1 type structural layer, and water molecules and exchangeable cations are arranged in interlayer domains. When high-temperature roasting is carried out, water molecules between layers are heated and gasified to generate pressure, so that the structure is quickly expanded, and the volume is accelerated to expand to form the expanded vermiculite. The vermiculite has rich negative charges between layers, and the main reason for the generation is Al existing in tetrahedral gaps in the structure3+、Fe3+Substituting for Si4+And the vermiculite structural layer is charged with redundant negative charges. In addition, part of water molecules between layers surround cations between layers to form coordination octahedrons, and occupy specific positions in the structure, and part of water molecules are in a free state. The structural characteristics enable the vermiculite to have stronger adsorption performance and cation exchange capacity, and is an excellent green catalyst carrier. The vermiculite modified by the sulfuric acid can dissolve out pore particle impurities and increase the specific surface area through ion exchange, and can form broken bonds of-Al-OH, -Si-OH and the like with Bronsted activity, and the broken bonds have strong adsorption performance and are favorable for strong adsorption of active components.
Disclosure of Invention
The invention aims to overcome the defects that the catalyst is difficult to separate, the equipment is corroded, the environment is polluted and the like in the traditional preparation process of cyclohexene, and provides a vermiculite supported phosphotungstic acid green catalyst which is convenient to recycle.
In order to achieve the purpose, the invention provides the following technical scheme: the catalyst takes vermiculite as a carrier, takes one of sodium hexametaphosphate, sodium phosphate and sodium silicate as a binder, and the phosphotungstic acid is loaded on the carrier to form the solid heteropoly acid catalyst, wherein the loading capacity of the phosphotungstic acid is 20-80%.
Preferably, the carrier vermiculite is high-temperature roasted expanded vermiculite (200-1000 ℃) and the Cation Exchange Capacity (CEC) of the carrier vermiculite is 0.998 mmol/g.
Preferably, the cation exchange modification treatment is carried out by using 2 mol/L sulfuric acid before use.
Preferably, the preparation method of the vermiculite supported phosphotungstic acid green catalyst comprises the following steps: (1) dissolving 0.1-0.5 g of binder in 2 mol/L of one of phosphoric acid, nitric acid, sulfuric acid, hydrochloric acid and oxalic acid, wherein the dosage of the binder is 10 ml, and then stirring for 10 min at room temperature by magnetic force until the binder is completely dissolved;
(2) adding 1 g of the high-temperature roasted modified vermiculite powder as shown in the claim 2 into the acid solution obtained in the step (1), and stirring for 1 hour at room temperature to uniformly mix the powder;
(3) dissolving 0.2-0.8 g of phosphotungstic acid in 5 ml of deionized water, adding the mixture obtained in the step (2) after complete dissolution, and stirring in an oil bath at 80 ℃ for 12 hours;
(4) stirring the mixed solution obtained in the step (3) in a water bath at 100 ℃ and evaporating to dryness, and then drying in an oven at 100 ℃ for 6 hours;
(5) and (4) roasting the powder obtained in the step (4) in a muffle furnace at 200 ℃ for 4 h to obtain the phosphotungstic acid supported catalyst.
Preferably, the high-temperature roasted vermiculite used in the step (2) is 80 meshes and is produced in Yuli county in Xinjiang.
Preferably, 0.4 to 1 g of the catalyst prepared in the claim 4 is placed in a single-neck flask with a fractionating column and a thermometer, 10 ml of cyclohexanol is added and stirred uniformly at room temperature, the mixture is stirred in an oil bath at 180 ℃ for reaction, a distillate is collected to separate a water layer, anhydrous calcium chloride is used for removing moisture of an organic layer, and a fraction at 80 to 85 ℃ is collected by atmospheric distillation to obtain a colorless and transparent cyclohexene product with pungent smell.
Compared with the prior art, the invention has the beneficial effects that:
1. compared with the traditional catalyst concentrated sulfuric acid, the catalyst has higher catalytic activity, the highest yield is 93.70 percent, and the dosage of the catalyst is 0.6 g.
2. The prepared catalyst is a solid supported catalyst, is applied to a heterogeneous reaction system, and is easy to separate and purify and reuse after the reaction is finished.
3. The prepared catalyst loaded active component is phosphotungstic acid, has small influence on equipment and environment, and is a green and environment-friendly catalyst.
4. The carrier vermiculite has larger crystal grains and specific surface area and is high-temperature resistant, so that the supported catalyst has high-temperature sintering resistance.
5. The vermiculite carrier has cation exchange performance, so that the surface of the carrier modified by sulfuric acid has broken bonds of-Al-OH, -Si-OH and the like with Bronst activity, has strong adsorption effect on active components, and improves the stability of the catalyst.
6. The phosphotungstic acid supported catalyst active component prepared by the over-volume impregnation method has higher dispersity, so that the loss of the active component and high-temperature sintering are weakened.
7. The binder is introduced in the preparation process of the catalyst, so that the problem of low load capacity only depending on the adsorption effect of the catalyst carrier is solved.
Detailed Description
The technical solution of the present invention will be clearly and completely described with reference to the following specific examples. The described embodiments are only some embodiments of the present invention, and all other embodiments obtained by those skilled in the art without any inventive work are within the scope of the present invention.
The invention provides a technical scheme that: the catalyst takes vermiculite as a carrier, takes one of sodium hexametaphosphate, sodium phosphate and sodium silicate as a binder, and the phosphotungstic acid is loaded on the carrier to form the solid heteropoly acid catalyst, wherein the loading capacity of the phosphotungstic acid is 20-80%.
The carrier vermiculite is high-temperature roasted expanded vermiculite (200-1000 ℃), and the Cation Exchange Capacity (CEC) of the carrier vermiculite is 0.998 mmol/g.
Before use, the cation exchange modification treatment is carried out by using 2 mol/L sulfuric acid.
The preparation method of the vermiculite supported phosphotungstic acid green catalyst comprises the following steps:
(1) dissolving 0.1-0.5 g of binder in 2 mol/L of one of phosphoric acid, nitric acid, sulfuric acid, hydrochloric acid and oxalic acid, wherein the dosage of the binder is 10 ml, and then stirring for 10 min at room temperature by magnetic force until the binder is completely dissolved;
(2) adding 1 g of the high-temperature roasted modified vermiculite powder as shown in the claim 2 into the acid solution obtained in the step (1), and stirring for 1 hour at room temperature to uniformly mix the powder;
(3) dissolving 0.2-0.8 g of phosphotungstic acid in 5 ml of deionized water, adding the mixture obtained in the step (2) after complete dissolution, and stirring in an oil bath at 80 ℃ for 12 hours;
(4) stirring the mixed solution obtained in the step (3) in a water bath at 100 ℃ and evaporating to dryness, and then drying in an oven at 100 ℃ for 6 hours;
(5) and (4) roasting the powder obtained in the step (4) in a muffle furnace at 200 ℃ for 4 h to obtain the phosphotungstic acid supported catalyst.
The high-temperature roasted vermiculite used in the step (2) is 80 meshes and is produced in Yuli county in Xinjiang.
Placing 0.4-1 g of the catalyst prepared in the claim 4 into a single-neck flask with a fractionating column and a thermometer, adding 10 ml of cyclohexanol, stirring uniformly at room temperature, stirring in an oil bath at 180 ℃, collecting a distillate, separating a water layer, removing water in an organic layer by using anhydrous calcium chloride, and collecting fractions at 80-85 ℃ by atmospheric distillation to obtain a colorless and transparent cyclohexene product with pungent smell.
Example 1
Preparation of the catalyst with a quantity of binder (AD) of 0.1 g: dissolving 0.1 g of binder in 2 mol/L acid, wherein the dosage is 10 ml, stirring at room temperature by magnetic force for 10 min until the binder is completely dissolved, adding 1 g of high-temperature roasted vermiculite powder, stirring at room temperature for 1h to mix the vermiculite powder uniformly, adding a phosphotungstic acid solution (0.6 g of phosphotungstic acid is dissolved in 5 ml of deionized water) prepared in advance, stirring in an oil bath at 80 ℃ for 12 h, then placing the mixture in a water bath at 100 ℃, stirring and evaporating to dryness, drying in an oven at 100 ℃ for 6 h, and roasting in a muffle furnace at 200 ℃ for 4 h to obtain a phosphotungstic acid supported catalyst PW, wherein the mark is 0.6-0.1AD/1 aEVM.
Example 2
Preparation of catalyst with binder amount of 0.2 g: wherein the binder was 0.2 g, and the other steps were as described in example 1 and labeled PW0.6-0.2AD/1 aEVM.
Example 3
Preparation of catalyst with binder amount of 0.3 g: wherein the binder was 0.3 g, and the other steps were as described in example 1 and labeled PW0.6-0.3AD/1 aEVM.
Example 4
Preparation of catalyst with binder amount of 0.4 g: the binder was 0.4g, and the other steps were as described in example 1 and labeled PW0.6-0.4AD/1 aEVM.
Example 5
Preparation of catalyst with binder amount of 0.5 g: wherein the binder was 0.5 g, and the other steps are as described in example 1 and labeled PW0.6-0.5AD/1 aEVM.
Examples 6 to 10
Experiment of the effect of different amounts of binder on catalytic activity: the catalytic activity of the supported catalysts with different AD contents prepared in examples 1 to 5 on the dehydration reaction of cyclohexanol was evaluated by the following method.
Putting 0.6 g of the prepared catalyst into a single-neck flask with a fractionating column and a thermometer, adding 10 ml of cyclohexanol, stirring uniformly at room temperature, stirring in an oil bath at 180 ℃, collecting a distillate, separating a water layer, removing a plurality of layers of water by using anhydrous calcium chloride, and collecting fractions at 80-85 ℃ by normal pressure distillation to obtain a colorless and transparent cyclohexene product with pungent smell, wherein the specific cyclohexene yield is shown in table 1.
TABLE 1 Effect of different AD on cyclohexene Selectivity and yield
| Sample (I) | Cyclohexene selectivity (%) | Cyclohexene yield (%) |
| PW0.6-0.1AD/1aEVM | 100 | 72.77 |
| PW0.6-0.2AD/1aEVM | 100 | 80.58 |
| PW0.6-0.3AD/1aEVM | 100 | 93.70 |
| PW0.6-0.4AD/1aEVM | 100 | 85.44 |
| PW0.6-0.5AD/1aEVM | 100 | 75.32 |
Example 11
The preparation method of the catalyst with the phosphotungstic acid loading of 0.2 g comprises the following steps: dissolving 0.3 g of AD in 2 mol/L acid, wherein the dosage is 10 ml, stirring at room temperature by magnetic force for 10 min until the AD is completely dissolved, adding 1 g of high-temperature roasted vermiculite powder, stirring at room temperature for 1h to mix uniformly, then adding a phosphotungstic acid solution (0.2 g of phosphotungstic acid is dissolved in 5 ml of deionized water) prepared in advance, stirring in an oil bath at 80 ℃ for 12 h, then placing in a water bath at 100 ℃, stirring and evaporating to dryness, drying in an oven at 100 ℃ for 6 h, and roasting in a muffle furnace at 200 ℃ for 4 h to obtain a phosphotungstic acid supported catalyst PW, wherein the PW is marked as 0.2-0.3AD/1 aEVM.
Example 12
The preparation method of the catalyst with the phosphotungstic acid loading of 0.4g comprises the following steps: the amount of phosphotungstic acid used was 0.4g, and the other steps were as described in example 11 and labeled PW0.4-0.3AD/1 aEVM.
Example 13
The preparation method of the catalyst with the phosphotungstic acid loading of 0.6 g comprises the following steps: the amount of phosphotungstic acid used was 0.6 g, and the other steps were as described in example 11 and labeled PW0.6-0.3AD/1 aEVM.
Example 14
The preparation method of the catalyst with the phosphotungstic acid loading of 0.8 g comprises the following steps: the amount of phosphotungstic acid used was 0.8 g, and the other steps were as described in example 11 and labeled PW0.8-0.3AD/1 aEVM.
Examples 15 to 18
Experiment of influence of different phosphotungstic acid loading amounts on catalyst activity: the catalytic activity of the catalysts with different phosphotungstic acid loads prepared in examples 11 to 14 on the dehydration reaction of cyclohexanol was evaluated by the following method.
Putting 0.6 g of the prepared catalyst into a single-neck flask with a fractionating column and a thermometer, adding 10 ml of cyclohexanol, stirring uniformly at room temperature, stirring in an oil bath at 180 ℃ for reaction, collecting a distillate, separating a water layer, removing a plurality of layers of water by using anhydrous calcium chloride, and collecting fractions at 80-85 ℃ by atmospheric distillation to obtain a colorless and transparent cyclohexene product with pungent smell, wherein the specific cyclohexene yield is shown in Table 2.
TABLE 2 Effect of different phosphotungstic acid loadings on cyclohexene selectivity and yield
| Sample (I) | Cyclohexene selectivity (%) | Cyclohexene yield (%) |
| PW0.2-0.3AD/1aEVM | 100 | 77.23 |
| PW0.4-0.3AD/1aEVM | 100 | 86.79 |
| PW0.6-0.3AD/1aEVM | 100 | 93.70 |
| PW0.8-0.3AD/1aEVM | 100 | 85.07 |
Example 19
Experiment of catalytic activity influence by different catalyst dosages: the catalytic activity of the catalyst for dehydration of cyclohexanol was evaluated by the following methods using 0.4g, 0.6 g, 0.8 g, and 1 g of the catalyst, respectively.
Respectively putting 0.4g, 0.6 g, 0.8 g and 1 g of PW0.6-0.3AD/1aEVM catalyst prepared by the catalyst into a single-neck flask with a fractionating column and a thermometer, then adding 10 ml of cyclohexanol, stirring uniformly at room temperature, stirring in an oil bath at 180 ℃ for reaction, collecting a distillate, separating a water layer, removing a plurality of layers of water by using anhydrous calcium chloride, and collecting fractions at 80-85 ℃ by normal pressure distillation to obtain colorless and transparent cyclohexene products with pungent smell, wherein the specific cyclohexene yield is shown in Table 3.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
TABLE 3 Effect of different catalyst amounts on cyclohexene Selectivity and yield
| Amount of catalyst used (g) | Cyclohexene selectivity (%) | Cyclohexene yield (%) |
| 0.4 | 100 | 90.37 |
| 0.6 | 100 | 93.70 |
| 0.8 | 100 | 90.36 |
| 1 | 100 | 89.97 |
Claims (6)
1. The preparation and the application of the vermiculite supported phosphotungstic acid green catalyst are characterized in that: the catalyst takes vermiculite as a carrier, takes one of sodium hexametaphosphate, sodium phosphate and sodium silicate as a binder, and the phosphotungstic acid is loaded on the carrier to form the solid heteropoly acid catalyst, wherein the loading capacity of the phosphotungstic acid is 20-80%.
2. The preparation and the application of the vermiculite supported phosphotungstic acid green catalyst according to claim 1 are characterized in that: the carrier vermiculite is high-temperature roasted expanded vermiculite (200-1000 ℃), and the Cation Exchange Capacity (CEC) of the carrier vermiculite is 0.998 mmol/g.
3. The preparation and the application of the vermiculite supported phosphotungstic acid green catalyst according to claim 1 are characterized in that: before use, the cation exchange modification treatment is carried out by using 2 mol/L sulfuric acid.
4. The preparation and the application of the vermiculite supported phosphotungstic acid green catalyst according to claim 1 are characterized in that: the preparation method of the vermiculite supported phosphotungstic acid green catalyst comprises the following steps:
(1) dissolving 0.1-0.5 g of binder in 2 mol/L of one of phosphoric acid, nitric acid, sulfuric acid, hydrochloric acid and oxalic acid, wherein the dosage of the binder is 10 ml, and then stirring for 10 min at room temperature by magnetic force until the binder is completely dissolved;
(2) adding 1 g of the high-temperature roasted modified vermiculite powder as shown in the claim 2 into the acid solution obtained in the step (1), and stirring for 1 hour at room temperature to uniformly mix the powder;
(3) dissolving 0.2-0.8 g of phosphotungstic acid in 5 ml of deionized water, adding the mixture obtained in the step (2) after complete dissolution, and stirring in an oil bath at 80 ℃ for 12 hours;
(4) stirring the mixed solution obtained in the step (3) in a water bath at 100 ℃ and evaporating to dryness, and then drying in an oven at 100 ℃ for 6 hours;
(5) and (4) roasting the powder obtained in the step (4) in a muffle furnace at 200 ℃ for 4 h to obtain the phosphotungstic acid supported catalyst.
5. The preparation and application of the vermiculite supported phosphotungstic acid green catalyst according to claim 4 are characterized in that: the high-temperature roasted vermiculite used in the step (2) is 80 meshes and is produced in Yuli county in Xinjiang.
6. The preparation and the application of the vermiculite supported phosphotungstic acid green catalyst according to claim 4 comprise the following steps: placing 0.4-1 g of the catalyst prepared in the claim 4 into a single-neck flask with a fractionating column and a thermometer, adding 10 ml of cyclohexanol, stirring uniformly at room temperature, stirring in an oil bath at 180 ℃, collecting a distillate, separating a water layer, removing water in an organic layer by using anhydrous calcium chloride, and collecting fractions at 80-85 ℃ by atmospheric distillation to obtain a colorless and transparent cyclohexene product with pungent smell.
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